Compounds and methods for the production of long chain hydrocarbons from biological sources

ABSTRACT

The present invention is directed to the preparation of oxygenated, unsaturated hydrocarbon compounds, such as derivatives of furfural or hydroxymethyl furfural produced by aldol condensation with a ketone or a ketoester, as well as methods of deoxidatively reducing those compounds with hydrogen under acidic conditions to provide saturated hydrocarbons useful as fuels.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional Application Nos.61/534,496, filed Sep. 14, 2011, and 61/669,775, filed Jul. 10, 2012,the entireties of which are incorporated by reference herein.

GOVERNMENT RIGHTS

The United States government has rights in this invention pursuant toContract No. DE-AC52-06NA25396 between the United States Department ofEnergy and Los Alamos National Security, LLC for the operation of LosAlamos National Laboratory.

TECHNICAL FIELD

The present invention is directed to the preparation of oxygenated,unsaturated hydrocarbon compounds, as well as methods of deoxidativelyreducing those compounds to provide saturated hydrocarbons useful asfuels and chemical feedstocks.

BACKGROUND

Saturated hydrocarbons containing from about seven to about fifteencarbons, up to about twenty-six carbons are used as fuel, and othermaterials. Such hydrocarbons are typically extracted or generated frompetroleum, a non-renewable resource. Methods of generating fuel- andhigh-quality hydrocarbons from renewable sources are thus needed.

SUMMARY

The present invention is directed to methods of making compounds offormula I:

wherein R₁ is H or C₁₋₆alkyl; each R₂ is independently hydrogen orC₁₋₆alkyl; R₃ is H or C₁₋₆ alkyl; R₄ is H, C₁₋₆alkyl, or substitutedC₁₋₆alkyl; n is 1, 2, 3, or 4; and m is 1, 2, 3, or 4; comprisingreacting a compound of formula A

with a compound of formula B

in the presence of a catalyst, for a time and at a temperaturesufficient to provide the compound of formula I. Compounds of formula I,as well as methods of deoxidatively reducing compounds of formula I toproduce hydrocarbon fuels, are also described.

The invention is also directed to methods of making compounds of formulaII:

wherein R₃ is H or C₁₋₆alkyl; R₄ is H, C₁₋₆alkyl, or substitutedC₁₋₆alkyl; and R₅ is C₁₋₁₆alkyl; comprising reacting a compound offormula A

with a compound of formula C

in the presence of catalyst, for a time and at a temperature sufficientto provide the compound of formula II. Compounds of formula II, as wellas methods for deoxidatively reducing compounds of formula II to producehydrocarbon fuels, are also described.

The invention is also directed to methods of converting oxygenated,unsaturated hydrocarbons to saturated hydrocarbons, in particular,hydrocarbon fuels, comprising reacting the oxygenated, unsaturatedhydrocarbons with hydrogen under acidic conditions in the presence of acatalyst and a Lewis acid for a time and at a temperature sufficient toprovide the saturated hydrocarbon.

DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS

It has heretofore been discovered that oxygenated biorenewablefeedstocks obtained from mono-, di-, or polysaccharides can be used togenerate fuel- and high-quality saturated hydrocarbons using an aldolreaction to generate an oxygenated unsaturated hydrocarbon that can bedeoxidatively reduced to generate the fuel- and high-quality saturatedhydrocarbons. Bioderived compounds useful in the present inventioninclude, for example, 2, 3, 4, 5, and 6 carbon-containing compounds, forexample hydroxymethyl furfural, furfural, methyl furfural, ethyllevulinate, homo ethyl levinate, and decan-2-one.

The aldol reaction is known per se in the art and involves the reactionof an aldehyde-containing compound with a ketone-containing compound toform an α,β-unsaturated ketone-containing compound:

It has now been discovered that the aldol reaction can be exploited toproduce compounds having from seven to fifteen carbons using startingmaterials derived from saccharides, which are renewable resources. Theresulting aldol products can then be deoxidatively reduced to producethe corresponding seven to fifteen carbon saturated hydrocarbons, whichare useful as fuels, for example.

One embodiment of the invention is directed to methods of makingcompounds of formula I:

wherein

-   -   R₁ is H or C₁₋₆alkyl;    -   each R₂ is independently hydrogen or C₁₋₆alkyl;    -   R₃ is H or C₁₋₆alkyl;    -   R₄ is H, C₁₋₆alkyl, or substituted C₁₋₆alkyl;    -   n is 1, 2, 3, or 4; and    -   m is 1, 2, 3, or 4; comprising:

reacting a compound of formula A

with a compound of formula B

in the presence of catalyst, for a time and at a temperature sufficientto provide the compound of formula I.

In preferred embodiments, the catalyst is a pyrrolidinium salt,preferably pyrrolidinium acetate.

The skilled person can readily determine an appropriate temperature forthe described methods of making compounds of formula I, nevertheless,temperatures from about ambient temperature to about 200° C. arepreferred, with ambient temperature being most preferred.

The skilled person can readily determine an appropriate time for themethods of making compounds of formula I, nevertheless, reaction timesof from about 1 hour to about 48 hours are preferred. More preferred arereaction times of from about 6 hours to about 48 hours. Even morepreferred are reaction times of from about 6 hours to about 24 hours.

The described methods are preferably performed in the absence ofsolvent, that is “neat.” Solvents can be employed, however. Preferredsolvents include tetrahydrofuran, ethyl acetate, alkyl alcohols, forexample, methanol, ethanol, propanol, isopropanol, butanol, and thelike, diethyl ether, methylene chloride, water, or a combinationthereof.

It is also preferred that the methods be performed wherein neither thecompound of formula A nor the compound of formula B is in excess. Thatis, in a preferred embodiment, the molar ratio of the compound offormula A to the compound of formula B is about 1:1.

In preferred embodiments, R₁ is C₁₋₄alkyl. In other preferredembodiments, R₁ is C₁₋₃alkyl. In other preferred embodiments, R₁ ismethyl or ethyl. In other embodiments, R₁ is H.

In preferred embodiments, R₂ is H. In other preferred embodiments, R₂ isC₁₋₄ alkyl. In other preferred embodiments, R₂ is C₁₋₃alkyl. In yetother embodiments, R₂ is C₁₋₂ alkyl. In still other embodiments, R₂ ismethyl.

In preferred embodiments, R₄ is hydrogen. In other embodiments, R₄ isC₁₋₄alkyl. In other preferred embodiments, R₄ is C₁₋₃alkyl. In yet otherembodiments, R₄ is C₁₋₂alkyl. In still other embodiments, R₄ is methyl.In other embodiments, R₄ is substituted C₁₋₆alkyl. In such embodiments,it is preferably that R₄ is C₁₋₆alkyl substituted with —OH. Preferably,R₄ is —CH₂—OH. Also preferred is where R₄ is —CH₂—CH₂—OH. R₄ can also beC₁₋₆alkyl substituted with oxo or —COOH.

In preferred embodiments, n is 1, 2, or 3. In other embodiments, n is 1.In yet other embodiments, n is 2. In still other embodiments, n is 3.

In preferred embodiments, m is 1, 2, or 3. In other embodiments, m is 1.In yet other embodiments, m is 2. In still other embodiments, m is 3.

In preferred embodiments, the compound of formula A is

Preferably, the compound of formula B is

Also preferred is where the compound of formula B is

Also within the scope of the invention is conversion of the compounds offormula I to the corresponding saturated hydrocarbon using deoxidativereducing conditions. The deoxidative reducing conditions can either beaccording to the methods described herein or can be according to methodsknown to those skilled in the art.

Compounds of formula I are also within the scope of the invention:

wherein

-   -   R₁ is H or C₁₋₆alkyl;    -   each R₂ is independently hydrogen or C₁₋₆alkyl;    -   R₃ is H or C₁₋₆alkyl;    -   R₄ is H, C₁₋₆alkyl, or substituted C₁₋₆alkyl;    -   n is 1, 2, 3, or 4; and    -   m is 1, 2, 3, or 4;    -   with the proviso that when R₁ is H, R₄ is C₁₋₆alkyl or        substituted C₁₋₆alkyl.

In preferred embodiments of compounds of formula I, R₁ is C₁₋₄alkyl. Inother preferred embodiments, R₁ is C₁₋₃alkyl. In other preferredembodiments, R₁ is methyl or ethyl. IN still other embodiments, R₁ is H.

In preferred embodiments of compounds of formula I, R₂ is H. In otherpreferred embodiments, R₂ is C₁₋₄alkyl. In other preferred embodiments,R₂ is C₁₋₃alkyl. In yet other embodiments, R₂ is C₁₋₂alkyl. In stillother embodiments, R₂ is methyl.

In preferred embodiments of compounds of formula I, R₄ is hydrogen. Inother embodiments, R₄ is C₁₋₄alkyl. In other preferred embodiments, R₄is C₁₋₃alkyl. In yet other embodiments, R₄ is C₁₋₂alkyl. In still otherembodiments, R₄ is methyl. In other embodiments, R₄ is substitutedC₁₋₆alkyl. In such embodiments, it is preferably that R₄ is C₁₋₆alkylsubstituted with —OH. Preferably, R₄ is —CH₂—OH. Also preferred is whereR₄ is —CH₂—CH₂—OH. R₄ can also be C₁₋₆alkyl substituted with oxo or—COOH.

In preferred embodiments of compounds of formula I, n is 1, 2, or 3. Inother embodiments, n is 1. In yet other embodiments, n is 2. In stillother embodiments, n is 3.

In preferred embodiments of compounds of formula I, m is 1, 2, or 3. Inother embodiments, m is 1. In yet other embodiments, m is 2. In stillother embodiments, m is 3.

Compounds of formula I are useful in the production of the correspondingsaturated hydrocarbons. Compounds of formula I can be converted to thecorresponding saturated hydrocarbon, preferably a fuel, usingdeoxidative reducing conditions. The deoxidative reducing conditions caneither be according to the methods described herein or can be accordingto methods known to those skilled in the art.

Also within the scope of the invention are methods for convertingcompounds of formula I

wherein

-   -   R₁ is H or C₁₋₆alkyl;    -   each R₂ is independently hydrogen or C₁₋₆alkyl;    -   R₃ is H or C₁₋₆alkyl;    -   R₄ is H, C₁₋₆alkyl, or substituted C₁₋₆alkyl;    -   n is 1, 2, 3, or 4; and    -   m is 1, 2, 3, or 4;        to fuels, which are preferably the corresponding saturated        hydrocarbons. These methods comprise deoxidatively reducing the        compound of formula I, preferrably using hydrogenation        conditions such as those described herein or known to those        skilled in the art.

Methods of making compounds of formula II are also within the scope ofthe invention:

wherein

R₃ is H or C₁₋₆alkyl;

R₄ is H, C₁₋₆alkyl, or substituted C₁₋₆alkyl; and

R₅ is C₁₋₁₆alkyl;

comprising:

reacting a compound of formula A

with a compound of formula C

in the presence of catalyst, for a time and at a temperature sufficientto provide the compound of formula II.

In preferred embodiments, the catalyst is a pyrrolidinium salt,preferable pyrrolidinium acetate.

The skilled person can readily determine an appropriate temperature forthe described methods for making compounds of formula II, nevertheless,temperatures from about ambient temperature to about 200° C. arepreferred, with ambient temperature being most preferred.

The skilled person can readily determine an appropriate time for themethods for making compounds of formula II, nevertheless, reaction timesof from about 1 hour to about 48 hours are preferred. More preferred arereaction times of from about 6 hours to about 48 hours. Even morepreferred are reaction times of from about 6 hours to about 24 hours.

The method is preferably performed in the absence of solvent, that is“neat.” Solvents can be employed, however. Preferred solvents includetetrahydrofuran, ethyl acetate, alkyl alcohols, for example, methanol,ethanol, propanol, isopropanol, butanol, and the like, diethyl ether,methylene chloride, water, or a combination thereof.

It is also preferred that the methods for making compounds of formula IIbe performed wherein neither the compound of formula A nor the compoundof formula C is in excess. That is, in a preferred embodiment, the molarratio of the compound of formula A to the compound of formula C about1:1.

In preferred embodiments, R₄ is hydrogen. In other embodiments, R₄ isC₁₋₄ alkyl. In other preferred embodiments, R₄ is C₁₋₃alkyl. In yetother embodiments, R₄ is C₁₋₂alkyl. In still other embodiments, R₄ ismethyl. In other embodiments, R₄ is substituted C₁₋₆alkyl. In suchembodiments, it is preferably that R₄ is C₁₋₆alkyl substituted with —OH.Preferably, R₄ is —CH₂—OH. Also preferred is where R₄ is —CH₂—CH₂—OH. R₄can also be C₁₋₆alkyl substituted with oxo or —COOH.

In preferred embodiments, R₅ is C₁₋₈ alkyl. In other preferredembodiments, R₅ is C₁₋₇alkyl. In other preferred embodiments, R₅ isC₁₋₆alkyl. In other preferred embodiments, R₅ is C₁₋₅alkyl. In otherpreferred embodiments, R₅ is C₁₋₄alkyl. In other preferred embodiments,R₅ is C₁₋₃alkyl. In other preferred embodiments, R₅ is C₁₋₂alkyl. Inother preferred embodiments, R₅ is methyl.

In preferred embodiments, the compound of formula A is

Preferably, the compound of formula C is

It is also within the scope of the invention that the compound offormula II be converted to the corresponding saturated hydrocarbon, thatis, fuel, using deoxidative reducing conditions. The deoxidativereducing conditions can either be according to the methods describedherein or can be according to methods known to those skilled in the art.

Also within the scope of the invention are methods of converting anoxygenated, unsaturated hydrocarbon or oxygenated, saturated hydrocarbonto a saturated hydrocarbon comprising reacting the oxygenated,unsaturated hydrocarbon or the oxygenated, saturated hydrocarbon withhydrogen under acidic conditions in the presence of a catalyst and aLewis acid for a time and at a temperature sufficient to provide thesaturated hydrocarbon.

The oxygenated, unsaturated hydrocarbon or oxygenated, saturatedhydrocarbon can be any oxygenated, unsaturated hydrocarbon oroxygenated, saturated hydrocarbon known in the art. Preferably, theoxygenated, unsaturated hydrocarbons of the invention include from 1 to5 double bonds, preferably 1 to 4 double bonds, more preferably 1 to 3double bonds. Oxygenated, unsaturated hydrocarbons within the scope ofthe invention can also have one or two double bonds.

“Oxygenated, saturated hydrocarbons,” as used herein refers to compoundshaving no aromatic double bonds. Such compounds may include unsaturated,aromatic groups such as heterocycles, for example, furans.

The oxygenated, unsaturated hydrocarbon or oxygenated, saturatedhydrocarbon can also have any number of oxygens, present in the compoundas an ether, ketone, ester, or saturated or unsaturated heterocycle.Preferably, the oxygenated, unsaturated hydrocarbon or oxygenated,saturated hydrocarbon will have from 1 to 10 oxygen atoms, morepreferably 1 to 8 oxygen atoms, even more preferably 1 to 6 oxygenatoms. Also preferred are compounds containing 1 to 4 oxygen atoms.

Preferred oxygenated, unsaturated hydrocarbons can be, for example, anyof the oxygenated unsaturated hydrocarbons described herein or known inthe art. Preferred oxygenated, unsaturated hydrocarbons include:

wherein

R₁ is H or C₁₋₆alkyl;

R₄ is H, C₁₋₆alkyl, or substituted C₁₋₆alkyl; and

R₅ is C₁₋₁₆alkyl.

Preferred oxygenated, saturated hydrocarbons can be, for example, any ofthe oxygenated saturated hydrocarbons described herein or known in theart. Preferred oxygenated, saturated hydrocarbons include:

Preferably, the methods for converting an oxygenated, unsaturatedhydrocarbon or oxygenated, saturated hydrocarbon to a saturatedhydrocarbon are performed under acidic conditions. Acidic conditions,known to those skilled in the art to have a pH of from less than 1 toless than 7, can be obtained using methods known to those skilled in theart. Preferably, the acidic conditions are obtained using a protic acid.Preferably, the protic acid is acetic acid, hydrochloric acid, nitricacid, formic acid, sulfuric acid, trifluoromethanesulfonic acid, andcombinations thereof.

The hydrogen can be applied at either atmospheric pressure at pressuresabove atmospheric pressure. For example, preferred pressures of hydrogenare from about 15 psi to about 500 psi, with about 100 psi being mostpreferred.

Those skilled in the art can determine a suitable temperature for themethods for converting an oxygenated, unsaturated hydrocarbon oroxygenated, saturated hydrocarbon to a saturated hydrocarbon, however,temperatures of from about ambient temperature to about 500° C. arepreferred. Preferably, the method is performed at about 200° C.

In preferred embodiments, the catalyst is a metal catalyst. Preferredmetals include palladium, platinum, iron, cobalt, copper, chromium, ornickel. Catalysts comprising these metals are known in the art. Apreferred catalyst is Pd/C. The skilled person can determine a suitableamount of catalyst needed to perform the method.

Any Lewis acid will be suitable for the methods of the invention,however Lewis acids of the formula Ln(X)n wherein Ln is a lanthanoid; Xis halide, triflate, bis(triflamide), C₁₋₆alkyl, aryl, amine, oxide,C₁₋₆alkoxide, or aryloxide; and n is 2 or 3 are preferred. A preferredLewis acid in La(OTf)₃. Other Lewis acids include ZnCl₂, ZrCl₄, andBiCl₃.

Also within the scope of the invention are methods of hydrogenating thedouble bonds of the α,β-unsaturated ketones of the compounds of formulaI of the invention to produce compounds of formula III. Such methods canbe accomplished using the procedure depicted in the following scheme,wherein R₄ of the compound of formula I is hydrogen:

The reaction depicted in Scheme 1 can be performed in any solvents, forexample, tetrahydrofuran, ethyl acetate, acetone, alkyl alcohols, forexample, methanol, ethanol, propanol, isopropanol, butanol, and thelike, diethyl ether, methylene chloride, water, or a combinationthereof.

Compounds of formula III can be deoxidatively reduced to fuels, that is,saturated hydrocarbons, using methods known in the art or using methodsdescribed herein.

A particularly preferred compound of formula III is

The resulting compounds of formula III can be further subject to chainelongation using methods known in the art. For example, compounds offormula III can be reacted with anhydrides according to the followingscheme to produce compounds of formula IV:

wherein

R₁ is H or C₁₋₆alkyl;

each R₂ is independently hydrogen or C₁₋₆alkyl;

R₃ is H or C₁₋₆alkyl;

n is 1, 2, 3, or 4;

m is 1, 2, 3, or 4; and

R is C₁₋₆alkyl.

As such, methods of the invention include reacting a compound of formulaIII

with an anhydride of the formula R—C(O)—O—C(O)—R in the presence of aLewis acid, for a time and at a temperature sufficient to produce thecompound of formula IV. Chain elongation of compounds of formula III viareaction with anhydrides can be accomplished according to the Scheme 2.

Those skilled in the art can readily identify suitable anhydrides foruse in the reaction depicted in Scheme 2. Those skilled in the art canalso readily identify suitable Lewis acids. Particularly preferred Lewisacids for chain elongation include, for example, ZnCl₂, FeCl₃*6H₂O,FeCl₃, ZrCl₄, CuCl₂, AlCl₃, and Yb(triflate)₃. Suitable solvents canalso be readily identified with preferred solvents including, forexample, tetrahydrofuran, ethyl acetate, acetone, acetonitrile, diethylether, methylene chloride, or a combination thereof.

Compounds of formula IV can be deoxidatively reduced to fuels, that is,saturated hydrocarbons, using methods known in the art or using methodsdescribed herein.

A particularly preferred compound of formula IV is:

Alternatively, compounds of formula III can chain elongated by reactionwith methyl vinyl ketone or acrolein according to produce compounds offormula V:

wherein

R₁ is H or C₁₋₆alkyl;

each R₂ is independently hydrogen or C₁₋₆alkyl;

R₃ is H or C₁₋₆alkyl;

n is 1, 2, 3, or 4;

m is 1, 2, 3, or 4; and

R₆ is H or C₁₋₂alkyl.

As such, methods of the invention include reacting a compound of formulaIII

with a compound of formula

in the presence of a Lewis acid or protic acid, for a time and at atemperature sufficient to produce a compound of formula V. PreferredLewis acids include, for example, FeCl₃. An exemplary method ofproducing compounds of formula V is depicted in Scheme 3.

Other preferred reactants include Lewis acids and protic acids, forexample, p-toluenesulfonic acid, NaHSO₃, AlCl₃, and ZrCl₄. Suitablesolvents can also be readily identified with preferred solventsincluding, for example, tetrahydrofuran, acetonitrile, ethyl acetate,acetone, diethyl ether, methylene chloride, or a combination thereof.

Compounds of formula V can be deoxidatively reduced to fuels, that is,saturated hydrocarbons, using methods known in the art or using methodsdescribed herein.

Particularly preferred compounds of formula V are

Also within the scope of the invention are methods of chain elongatingcompounds of formula III to produce compounds of formula IV:

wherein

R₁ is H or C₁₋₆alkyl;

each R₂ is independently hydrogen or C₁₋₆alkyl;

R₃ is H or C₁₋₆alkyl;

n is 1, 2, 3, or 4;

m is 1, 2, 3, or 4; and

z is 1 to 7.

These methods include reacting a compound of formula III

with maleic anhydride, an anhydride of the formula

maleic acid, fumaric acid, muconic acid, 2,5-furan dicarboxylic acid, ora dicarboxylic acid of the formula

in the presence of a Lewis acid or dehydrating agent; for a time and ata temperature sufficient to produce the compound of formula VI.

In preferred embodiments, the anhydride of the formula

is succinic anhydride, glutaric anhydride, adipic anhydride, pimelicahydride, suberic anhydride, azelaic anhydride, or sebacic anhydride.

In other preferred embodiments, the dicarboxylic acid of the formula

is succinic acid, glutaric acid, adipic acid, pimelic acid, subericacid, azelaic acid, or sebacic acid.

Chain elongation of compounds of formula III can be accomplished byreaction with cyclic anhydrides according to Scheme 4 to producecompounds of formula VI

Preferred cyclic anhydrides include, for example, maleic anhydride,succinic anhydride, glutaric anhydride, adipic anhydride, pimelicahydride, suberic anhydride, azelaic anhydride, and sebacic anhydride.

Chain elongation of compounds of formula III can also be accomplished byreaction with dicarboxylic acids according to Scheme 5 to producecompounds of formula VI.

Preferred dicarboxylic acids include succinic acid, glutaric acid,adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid,maleic acid, fumaric acid, muconic acid, and 2,5-furan dicarboxylicacid. Preferred Lewis acids include, for example, AlCl₃ and thelanthanide triflates. Preferred dehydrating agents include protic acids,for example, sulfuric acid. Another preferred dehydrating agent is P₂O₅.

With certain dicarboxylic acids, it may be necessary to activate thedicarboxylic acid for reaction with a compound of formula III. Suchactivation is known to those skilled in the art and can includeactivation such as that shown in Scheme 6:

Within the scope of Scheme 6, examples of dicarboxylic acids (“DCAs”)include maleic, muconic, 2,5-furan dicarboxylic acid, fumaric acid, andthe like. Activating agents include, for example, Lewis acids anddehydrating acids. Muconic furan dicarboxylic acid and fumaric acid willnot form symmetrical anhydrides. These can be activated for theFriedel-Crafts reaction by converting the diacids to the mono ester acidchloride and used in the reaction scheme shown in Scheme 6.

Compounds of formula VI can be deoxidatively reduced to fuels, that is,saturated hydrocarbons, using methods known in the art or using methodsdescribed herein.

Scheme 7 depicts alternative methods of making compounds within thescope of the invention. Within the scope of Scheme 7, examples ofdicarboxylic acids (“DCAs”) include maleic, muconic, 2,5-furandicarboxylic acid, fumaric acid, and the like. Activating agents includeLewis acids and dehydrating acids, as described herein. Muconicdicarboxylic acid and fumaric acid will not form symmetrical anhydrides.These can be activated for the Friedel-Crafts reaction by converting thediacids to the mono ester acid chloride and used in the reaction schemeshown in Scheme 7.

Compounds within the scope of the invention can be reductivelydeoxygenated according to, for example, Scheme 8.

As used herein, “alkyl” refers to a branched or straight chain saturatedaliphatic hydrocarbon radical of from 1 to 20 carbons, i.e., C₁₋₂₀alkyl.The term alkyl includes, but is not limited to, radicals such as methyl,ethyl propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl,undecyl, docecyl, and the like. Branked alkyl radicals include, forexample, isobutyl, tert-butyl, isopropyl, and the like.

As used herein, “substituted alkyl” refers to and alkyl radical whereinone, two or three hydrogens has been replaced with a functional group.Preferred functional groups include —OH, halogen (F, Cl, Br), oxo (═O),alkoxy (alkyl-O—), —COOH, and the like.

As used herein, “deoxidative reduction” refers to a process whereinreductive conditions are employed that not only reduce the compound ofinterest, but also deoxygenate the compound of interest.

As used herein, “hydrocarbon” refers to an organic compound wherein themajority of the atoms in the compound are carbon and hydrogen. In an“oxygenated hydrocarbon,” within the scope of the invention, themajority of the atoms in the compound are carbon and hydrogen, with aminority of the atoms of the compound being oxygen.

As used herein, “saturated hydrocarbon” refers to organic compoundswherein the majority of the atoms in the compound are carbon andhydrogen and all bonds within the compound are single bonds.

As used herein, “unsaturated hydrocarbon” refers to organic compoundswherein the majority of the atoms in the compound are carbon andhydrogen and wherein at least one bond within the compound is a doublebond.

Hydrogenation reactions described herein were carried out in a 50 mLAutoclave Engineers, high-pressure reactor connected to the custom-buildhydrogen supply and uptake measurement system, allowing for real-timemeasurement of hydrogen uptake at constant pressure (dynamic mode) orthe determination of the total amount of hydrogen consumed aftercompletion of the reaction (totalizer mode) using a thermal mass flowmeter.

In dynamic mode the reactor is charged with substrate, solvent (whereapplicable) and catalyst encapsulated in a sealed glass ampoule. Thereactor is then sealed, pressurized to the desired level with an openconnection and heated to the set temperature. The reaction is thenstarted by switching on the stirrer in the reactor, shattering the glassampoule and releasing the catalyst (time=0) with immediate measurementof the hydrogen uptake rate. Since the relative volume of the reservoirs(7570 mL=2 US gallons) is 300 times that of the head space of thereactor (25 mL) and total substrates amounts can be adjusted as desiredlimiting total hydrogen consumption. The reaction order of hydrogenitself (by definition=0 in any given run in this method) can then bedetermined by carrying out experiments at different hydrogen pressuresall other parameters being equal.

In totalizer mode, the reactor is charged with substrate, solvent (whereapplicable) and catalyst, pressurized from the reservoirs to the desiredlevel and then isolated from the hydrogen feed system. The reaction isthen started by switching on the heater and stirrer. In this case thepressure in the reactor will drop as hydrogen is consumed. Completion ofthe reaction is indicated by reaching a constant pressure as indicatedby the pressure gauge. Upon completion the reactor is allowed to cool toambient temperature and then re-pressurized to the starting pressure

For both methods the actual moles of hydrogen gas consumed weredetermined by applying the virial gas theorem, i.e., an expanded idealgas law as

$Z = {\frac{{PV}_{m}}{RT} = {1 + \frac{B}{V_{m}} + \frac{C}{V_{m}^{2}} + \ldots}}$

where B=14.38 cm³/mol and C=370 cm³/mol (at standard conditions—seelines 7 & 8 of Chart 2; Lit.: Michels, A. D. G., W.; Ten Seldam, C. A.Physica 1960, 393.) are the second and third virial coefficients, V_(m)is the molar volume, and Z is the compression factor. Note that in bothmethods the actual measurement of the gas flow is carried out at theambient temperature of the mass flow meter, which is calibrated for atemperature of 293.15 K and a pressure of 1013.25 bar or 14.69595025 psiregardless of the reaction temperature and pressure.

EXAMPLES Example 1 Preparation of (E)-ethyl7-(5-(hydroxymethyl)furan-2-yl)-5-oxohept-6-enoate

In a 250 mL ground glass single necked, 24/40, round bottom flask wasplaced 30 g of hydroxymethyl furfural (HMF) (238 mmol), 38.4 g ofhomoethyllevulinate (243 mmol) and 35 mL of ethanol. Stirring wasstarted and the system was purged with argon. To this mixture, atambient temperature, was added 2 mL of pyrrolidine (23.9 mmol). Duringthe addition, the mixture darkened. Once the mixture was mixed well, itwas then chilled using an ice bath. Once the mixture had obtained atemperature of 5° C. or less, 7.14 mL of acetic acid was added dropwise(mixture was still over an atmosphere of argon). Once completed, the icebath was removed and the mixture stirred overnight. The reaction wasmonitored for completion by ¹H and ¹³C NMR spectroscopy (as determinedby disappearance of the aldehyde proton or carbon resonance). Oncedetermined to be complete (12 h for this reaction) the mixture wasplaced on a rotovap and the ethanol and water were mostly removed. Themixture was then chilled and cold water was added. A yellow solidprecipitated out and it was washed with cold water. The solids weredried under a vacuum to give 58.92 g of the product (93%). The waterwashings were extracted with ethyl acetate and about 3 more grams ofproduct was recovered. δ_(H) (CDCl₃) 1.25 (t, J=7 Hz, 3H), 2.0 (app p,J=7 Hz, 2H), 2.37 (t, J=7 Hz, 2H), 2.67 (t, J=7 Hz, 2H), 4.13 (q, J=7Hz, 2H), 4.65 (s, 2H), 6.39 (m, 1H), 6.62 (m, 2H), 7.28 (m, 1H). δ¹³_(C) (CDCl₃) 199.4, 173.5, 157.1, 150.96, 128.9, 123.1, 117.0, 110.6,60.6, 57.7, 40.4, 33.6, 19.6, 14.4.

Example 2 Preparation of (E)-ethyl7-(5-methylfuran-2-yl)-5-oxohept-6-enoate

In a 250 mL ground glass single necked, 24/40, round bottom flask wasplaced 40 g of methyl furfural (396 mmol), 62.6 g of homoethyllevulinate(396 mmol). Stirring was started and the system was purged with argon.To this mixture, at ambient temperature, was added 3.3 mL of pyrrolidine(39.5 mmol). During the addition, the mixture darkened. Once the mixturewas mixed well, it was then chilled using an ice bath. Once the mixturehad obtained a temperature of 5° C. or less, 6.0 mL of acetic acid wasadded dropwise (mixture was still over an atmosphere of argon). Oncecompleted, the ice bath was removed and the mixture stirred overnight.The reaction was monitored for completion by ¹H and ¹³C NMR spectroscopy(as determined by disappearance of the aldehyde proton or carbonresonance). Once determined to be complete (12 h for this reaction) themixture was placed on a rotovap and the ethanol and water were mostlyremoved. Purification by silica gel chromatography gave 90.66 g (95%).δ_(H) (CDCl₃) 1.25 (t, J=7 Hz, 3H), 1.98, (app p, J=7 Hz, 2H), 2.40 (s,3H), 2.37 (t, J=7 Hz, 2H), 2.65 (t, J=7 Hz, 2H), 4.17 (q, J=7 Hz, 2H),6.09 (s, 1H), 6.56 (m, 2H), 7.25 (m, 1H). δ¹³ _(C) (CDCl₃) 198.7, 172.9,155.4, 149.2, 128.4, 121.1, 117.3, 108.8, 59.9, 39.7, 33.0, 19.1, 13.8,13.5.

Example 3 Preparation of (E)-ethyl6-(5-(hydroxymethyl)furan-2-yl)-4-oxohex-5-enoate

11.3 mL of ethyl levulinate (79.2 mmol) was placed in a ground glasssingle necked, 24/40, round bottom flask and stirring was begun. Thiswas then chilled with an ice bath. In air, the pyrrolidine (1.25 mL,15.8 mmol) and acetic acid (0.91 mL, 15.8 mmol) was then added.Hydroxymethyl furfural (HMF) (10.01 g, 79.2 mmol) was then added andsolution darkened. The cooling bath was then removed and the solutionwas stirred at ambient temperature until the reaction was complete (by¹H and ¹³C NMR). The reaction was then purified by silica gelchromatography (using an ethyl acetate/hexane gradient). 17.1 g ofproduct was obtained (85%). δ_(H)(CDCl₃) 1.21 (t, J=7 Hz, 3H), 2.60 (t,J=6.6 Hz, 2H), 2.86 (t, J=6.6 Hz, 2H), 4.09 (q, J=7 Hz, 2H), 4.56 (s,2H), 6.19 (m, 1H), 6.56 (m, 2H), 7.25 (m, 1H). δ¹³ _(C) (CDCl₃) 197.6,172.6, 157.1, 150.0, 128.6, 120.0, 116.7, 109.8, 60.3, 56.8, 35.1, 27.8,13.6.

Example 4 Preparation of (E)-ethyl 6-(furan-2-yl)-4-oxohex-5-enoate

The same process was used as described for (E)-ethyl6-(5-(hydroxymethyl)furan-2-yl)-4-oxohex-5-enoate. (E)-ethyl6-(furan-2-yl)-4-oxohex-5-enoate can be distilled. Distillation yielded17.93 g (78%). δ_(H)(CDCl₃) 1.25 (t, J=7 Hz, 3H), 2.66 (t, J=6.6 Hz,2H), 2.94 (t, J=6.6 Hz, 2H), 4.12 (q, J=7 Hz, 2H), 6.48 (m, 1H), 6.65(m, 2H), 7.34 (d, J=16 Hz, 1H), 7.49 (d, J=1.5 Hz, 1H). δ¹³ _(C) (CDCl₃)197.2, 172.4, 150.5, 144.6, 128.5, 122.5, 115.4, 112.1, 60.15, 35.2,27.8, 13.7.

Example 5 Preparation of 1-(5-Hydroxymethyl-furan-2-yl)-undec-1-en-3-one

In a 50 mL ground glass, single necked, 14/20, round bottom flask wasplaced 0.138 mL of pyrrolidine (1.65 mmol) and 2 mL of ether. To thiswas added 0.094 mL of acetic acid. The mixture was chilled using an icebath. To this, 0.234 g of decane-2-one (1.5 mmol) was added as an ethersolution (2 mL) dropwise. The mixture was stirred for 30 min and 0.189 gof hydroxymethyl furfural (HMF) was added (1.5 mmol). The mixture wasthen warmed to ambient temperature and stirred for 48 h. Purificationusing silica gel chromatography yielded 0.2773 g of the product (70%yield). The proton and ¹³C NMR spectra were consistent with the assignedstructure.

This reaction was also performed by replacing the ether with THF andEtOH to yield similar results.

Example 6 Preparation of 1-Furan-2-yl-undec-1-en-3-one

1-Furan-2-yl-undec-1-en-3-one was prepared using a procedure similar tothat described for the synthesis of1-(5-Hydroxymethyl-furan-2-yl)-undec-1-en-3-one using either ethanol assolvent or using no solvent.

Example 7 General Procedure for the Conversion of Oxygenated,Unsaturated Hydrocarbons to Saturated Hydrocarbons

The oxygenated, unsaturated hydrocarbon is treated with hydrogen underpressures of about atmospheric pressure to about 500 psi, in thepresence of a catalyst, preferably Pd/C, and a Lewis acid, preferablyLa(OTf)₃, at a temperature of from ambient temperature to about 500° C.The reaction is carried out under acidic conditions, i.e., pH of lessthan 7, preferably in the presence of acetic acid. The reaction iscomplete in from about 5 minutes to about 48 hours.

Example 8 Preparation of n-Nonane

Compound 1 (0.25 g) was combined in acetic acid (1 mL) with Pd/C (10% bywt Pd, 0.125 g), La(OTf)₃ (0.100 g) and placed in a sealed vessel underH₂ pressure (100 psi). The vessel was heated to 200° C. for 15 hours.The heating source was removed and the vessel allowed to cool to roomtemperature. The pressure was released and reaction mixture extractedfrom the vessel with methylene chloride (2×2 mL) and water (2×2 mL). Thecombined layers were filtered and the organic layer separated, driedover NaSO₄ and solvent removed in vacuo yield n-nonane as a colorlessoil (67% isolated yield) as confirmed by GC-MS. ¹H NMR (400 MHz, CDCl₃)δ 1.29 (m, 14H), 0.88 (s, 6H). ¹³C NMR (101 MHz, CDCl₃) δ 32.14, 29.73,29.57, 22.81, 14.23.

Example 9 Preparation of n-Dodecane

Compound 2 (0.25 g) was combined in acetic acid (1 mL) with Pd/C (10% bywt Pd, 0.125 g), La(OTf)₃ (0.100 g) and placed in a sealed vessel underH₂ pressure (100 psi). The vessel was heated to 200° C. for 15 hours. Atthis time the heating source was removed and the vessel allowed to coolto room temperature. The pressure was released and reaction mixtureextracted from the vessel with methylene chloride (2×2 mL) and water(2×2 mL). The combined layers were filtered and the organic layerseparated, dried over NaSO₄ and solvent removed in vacuo to yieldn-dodecane as a colorless oil (76% isolated yield) as confirmed byGC-MS. ¹H NMR (400 MHz, CDCl₃) δ 1.27 (m, 20H), 0.88 (m, 6H). ¹³C NMR(101 MHz, CDCl₃) δ 32.11, 29.85, 29.58, 22.86, 14.19.

Example 10 Stepwise Preparation of n-Dodecane

Unsaturated C₁₂ (250 mg, 1.00 mmol) was dissolved in methanol (15 mL)and added to a round bottom flask containing wetted Pd/C (125 mg of 10wt % Pd/C, 0.120 mmol Pd, 12 mol % Pd relative to substrate). Themixture was put under 1 atmosphere of H₂ and heated at 60° C. for 1 hourto yield a pale yellow solution of saturated C12 as confirmed by NMR (¹HNMR (400 MHz, CDCl₃) δ 5.74 (d, 1H), 4.03 (q, J=7.1, 2H), 2.76 (t,J=7.3, 1H), 2.70-2.54 (m, 2H), 2.50-2.33 (m, 2H), 2.31-2.18 (m, 2H),2.14 (s, 2H), 2.11-1.99 (m, 1H), 1.88-1.71 (m, 2H), 1.16 (t, J=7.1, 3H).¹³C NMR (101 MHz, CDCl₃) δ 208.65, 173.00, 152.49, 150.33, 105.80,105.66, 60.18, 41.42, 40.82, 33.11, 22.11, 18.72, 14.08, 13.30).

HCl (1 mL) was added to the solution and the flask was then equippedwith a condenser, opened to the air and heated at 100° C. for 3 hours toyield a colorless solution. The solvent was removed and resultant solidextracted with dichloromethane (3×5 mL), dried over MgSO₄, filtered andsolvent removed in vacuo to yield the triketone acid (223 mg, 91% yield)(¹H NMR (400 MHz, CDCl₃) δ 2.71 (m, 8H), 2.54 (m, 3H), 2.35 (m, 3H),1.88 (m, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 208.54, 207.91, 206.90, 173.56,36.99, 36.11, 36.07, 36.03, 32.88, 30.89, 29.82, 18.57).

The triketone acid (245 mg, 0.91 mmol) was dissolved in 1M HCl (5 mL)and added along with Pd/C (245 mg of 10 wt % Pd/C, 0.230 mmol Pd, 23 mol% Pd relative to substrate) to a stainless steel Swagelok equippedsample tube. The tube was then pressurized with 300 psi H₂ and heated to200° C. for 14 hours. Upon cooling, the pressure was released andreaction mixture extracted from the vessel with methylene chloride (2×2mL) and water (2×2 mL). The combined layers were filtered and theorganic layer separated, dried over NaSO₄ and solvent removed in vacuoto yield dodecane as a colorless oil (118 mg, 76%) as confirmed byGC-MS. ¹H NMR (400 MHz, CDCl₃) δ 1.27 (m, 20H), 0.88 (m, 6H). ¹³C NMR(101 MHz, CDCl₃) δ 32.11, 29.85, 29.58, 22.86, 14.19.

Example 11 Preparation of n-Pentadecane

Compound 3 (0.25 g) was combined in acetic acid (1 mL) with Pd/C (10% bywt Pd, 0.250 g), La(OTf)₃ (0.200 g) and placed in a sealed vessel underH₂ pressure (100 psi). The vessel was heated to 200° C. for 15 hours. Atthis time the heating source was removed and the vessel allowed to coolto room temperature. The suspension was removed from the vessel anddiluted with dichloromethane and 2-propanol and filtered to remove thecatalyst. The solvent was removed under vacuum and redissolved inbenzene-d6. The pressure was released and reaction mixture extractedfrom the vessel with methylene chloride (2×2 mL) and water (2×2 mL). Thecombined layers were filtered and the organic layer separated, driedover NaSO₄ and solvent removed in vacuo to yield pentadecane as acolorless oil (65% isolated yield) as confirmed by GC-MS. ¹H NMR (400MHz, CDCl₃) δ 1.27 (m, 26H), 0.88 (m, 6H). ¹³C NMR (101 MHz, CDCl₃) δ32.09, 29.87, 29.53, 22.82, 14.15.

Example 12 Stepwise Preparation of n-Pentadecane

Unsaturated C₁₅ precursor (250 mg, 1.00 mmol) was dissolved in glacialacetic acid (15 mL) and added to a round bottom flask containing Pd/C(125 mg of 10 wt % Pd/C, 0.120 mmol Pd, 12 mol % Pd relative tosubstrate). The mixture was put under 1 atmosphere of H₂ and heated at100° C. for 12 hours to yield a pale yellow solution of pentaketone asconfirmed by NMR (¹H NMR (400 MHz, CDCl₃) δ 2.73 (m, 16H), 2.18 (s, 6H).¹³C NMR (101 MHz, CDCl₃) δ 207.93, 207.88, 207.18, 36.97, 36.11, 36.06,36.02, 29.85).

The solution was transferred to a stainless steel pressure reactor withLa(OTf)₃ (170 mg, 0.290 mmol) pressurized with 300 psi H₂ and heated to200° C. for 14 hours. Upon cooling, the pressure was released andreaction mixture extracted from the vessel with methylene chloride (2×2mL) and water (2×2 mL). The combined layers were filtered and theorganic layer separated, dried over NaSO₄ and solvent removed in vacuoto yield pentadecane as a colorless oil (97 mg, 65%) as confirmed byGC-MS. ¹H NMR (400 MHz, CDCl₃) δ 1.27 (m, 26H), 0.88 (m, 6H). ¹³C NMR(101 MHz, CDCl₃) δ 32.09, 29.87, 29.53, 22.82, 14.15.

Example 13 Preparation of Ethyl 6-(furan-2-yl)-4-oxohexanoate

In a round bottom flask was placed 1.334 g (6.000 mmol) of (E)-ethyl6-(furan-2-yl)-4-oxohex-5-enoate. 6 mL of acetonitrile was added andstirring was begun. To this was added 0.064 g Pd/C (en) and hydrogen wasadded using a balloon (˜1 atm). The reaction mixture was stirred for 48h and the mixture was then purified by flash column chromatography using15% ether/hexane, v/v. Purification gave rise to 0.4817 g (73%) of thesaturated system ¹H (CDCl₃) δ 1.25 (t, J=7 Hz, 3H), 2.6 (m, 2H), 2.8 (m,2H), 2.9 (m, 2H), 3.0 (m, 2H), 4.16 (q, J=7 Hz), 6.0 (1H), 6.3 (1H), 7.3(1H).

Example 14 Preparation of Ethyl 6-(5-acetylfuran-2-yl)-4-oxohexanoate

In a round bottom flask was placed 0.224 g (1.00 mmol) of ethyl6-(furan-2-yl)-4-oxohexanoate. 1 mL of acetonitrile was added andstirring was begun. To this was added 0.031 g (0.050 mmol) of ytterbiumtrifluoromethanesulfonate [Yb(OTf)₃] and 0.204 g (2.00 mmol) of aceticanhydride was added. The reaction mixture was stirred overnight and themixture was then purified by flash column chromatography using 30%ether/hexane, v/v. Purification gave rise to 0.1440 g (54%) of theacylated furan. δ ¹H (CDCl₃) 1.32 (t, J=7 Hz, 3H), 2.45 (s, 3H), 2.65(m, 2H), 2.8 (t, J=5 Hz, 2H), 2.9 (m, 2H), 3.0 (m, 2H), 4.16 (q, J=7Hz), 6.22 (d, J=3.5 Hz, 1H), 7.12 (d, J=3.5 Hz, 1H).

Example 15 Preparation of Ethyl4-oxo-6-(5-(3-oxobutyl)furan-2-yl)hexanoate

In a round bottom flask was placed 0.366 g (1.63 mmol) of ethyl6-(furan-2-yl)-4-oxohexanoate. 1.6 mL of acetonitrile was added andstirring was begun. To this was added 0.031 g (0.163 mmol) ofp-toluenesulfonic acid mono hydrate and 0.172 g (2.5 mmol) of methylvinyl ketone was added. The reaction mixture was stirred for 1 h and themixture was then purified by flash column chromatography using 25%ether/hexane, v/v. Purification gave rise to 0.2432 g (51%) of thealkylated furan. δ ¹H (CDCl₃) 1.25 (t, J=7 Hz, 3H), 2.16 (s, 3H), 2.6(m, 2H), 2.73-2.88 (m, 10H), 4.13 (q, J=7 Hz, 2H), 5.86 (s, 2H): δ ¹³C(CDCl₃) 14.4, 22.40, 22.49, 28.2, 30.2, 37.3 41.1, 42.0, 60.9, 106.0,153.2, 153.24, 173.0, 207.6, 207.7

Example 16

To a 50 mL round bottom flask, 0.5625 g (3.75 mmol) of unsaturated C₉precursorwas dissolved in a H₂O/HOAc mixture (50% by wt) acetic acid inH₂O (15 mL) and Pd/C added (13 mg of 5 wt % Pd/C, 0.006 mmol Pd, 0.16mol % Pd relative to substrate). The solution was added to a roundbottom flask, put under an atmosphere of H₂ using a balloon and heatedat 65° C. for 2-3 hours to yield a near colorless solution of thehydrogenated product.

Example 17

Unsaturated C₉ precursor (166 mg, 1.00 mmol) was dissolved in MeOH (1mL) and added dropwise to a stirred mixture of Mg turnings (49 mg, 2.0mmol) in MeOH (5 mL). On addition of A, gas evolution was observed and aprecipitate formed. Stirring was allowed to continue for 10 hours. Thesolution was filtered and solvent removed in vacuo to yield 98 mg of thesaturated C9 as a yellow powder (56% yield).

Unsaturated C₉ precursor (166 mg, 1.00 mmol) was dissolved in a 50% v/vsolution of acetic acid in H₂O (5 mL) containing ammonium formate (126mg, 2.00 mmol) and Pd/C (83 mg of 10 wt % Pd/C, 0.080 mmol Pd, 8 mol %Pd relative to substrate). The mixture was heated at 100° C. for 10hours, cooled to room temperature and filtered. The aqueous layer wasextracted with dichloromethane (3×5 mL), dried over MgSO₄, filtered andsolvent removed in vacuo to yield the saturated C9 (142 mg, 85% yield).

Unsaturated C₉ precursor (166 mg, 1.00 mmol) was dissolved in a 50% v/vsolution of acetic acid in H₂O (5 mL) and 5 wt % Pd/C (83 mg of 10 wt %Pd/C, 0.080 mmol Pd, 8 mol % Pd relative to substrate). The resultingmixture was added to a stainless steel sample tube, pressurized with H₂gas (100 psi) and heated at 60° C. for 10 hours, cooled to roomtemperature, the pressure released and the resultant mixture filtered.The aqueous layer was extracted with dichloromethane (3×5 mL), driedover MgSO₄, filtered and solvent removed in vacuo to yield the saturatedC9 (155 mg, 92% yield).

Unsaturated C₉ precursor (166 mg, 1.00 mmol) was dissolved in methanol(5 mL) and added to wetted Pd/C (83 mg of 10 wt % Pd/C, 0.080 mmol Pd, 8mol % Pd relative to substrate). The mixture was placed in a roundbottom flask and put under 1 atmosphere of H₂ gas and heated at 60° C.for 1 hour, cooled to room temperature and taken to dryness. The solidwas extracted with dichloromethane (3×5 mL), dried over MgSO₄, filteredand solvent removed in vacuo to yield the saturated C9 in quantitativeyield. ¹H NMR (400 MHz, CDCl₃) δ 6.00 (m, 2H), 4.48 (s, 2H), 3.22 (m,2H), 3.10-2.32 (m, 4H), 2.12 (s, 3H). ¹³C NMR (101 MHz, CDCl₃) δ 207.85,154.49, 152.80, 108.44, 105.96, 57.18, 41.58, 29.87, 22.18.

Example 18

The saturated C₉ species was dissolved in a H₂O/HOAc mixture (50% by wt)acetic acid in H₂O (15 mL) and a reflux condenser was attached to theround bottom flask. The reaction solution was heated to 100° C.overnight (˜12-14 h) to yield a dark orange/red solution to yield thetriketone in 98% isolated yield. ¹H NMR (400 MHz, CDCl₃) δ 2.92-2.44 (m,8H), 2.42-1.97 (m, 6H). ¹³C NMR (101 MHz, CDCl₃) δ 207.99, 207.30,36.99, 36.09, 29.87.

Example 19

Saturated C₉ precursor (0.168 g, 1.00 mmol) was dissolved in 50% v/vsolution of acetic acid (5 mL) in H₂O and placed in a round bottom flaskwith a condenser and heated at 100° C. for 3 hours to provide acolorless solution, that when cooled could be neutralized with NaHCO₃and extracted with dichloromethane (3×5 mL), dried over MgSO₄, filteredand solvent removed in vacuo to yield non-2,5,7-trione (166 mg, 98%yield).

Saturated C₉ precursor (0.168 g, 1.00 mmol) was dissolved in a 1Msolution of HCl in methanol (10 mL) and placed in a round bottom flaskwith a condenser and heated at 100° C. for 3 hours to provide acolorless solution. The solvent was removed and extracted withdichloromethane (3×5 mL), dried over MgSO₄, filtered and solvent removedin vacuo to yield non-2,5,7-trione in near quantitative yield. ¹H NMR(400 MHz, CDCl₃) δ 2.92-2.44 (m, 8H), 2.42-1.97 (m, 6H). ¹³C NMR (101MHz, CDCl₃) δ 207.99, 207.30, 36.99, 36.09, 29.87.

Example 20

Nona-2,5,7-trione (170 mg, 1.00 mmol) was dissolved in glacial aceticacid (5 mL) and added along with Pd (170 mg of 10 wt % Pd/C, 0.160 mmolPd, 16 mol % Pd relative to substrate) and La(OTf)₃ (170 mg, 0.290 mmol)to a stainless steel Swagelok equipped sample tube. The tube was thenpressurized with 100 psi H₂ and heated to 225° C. for 14 hours. Uponcooling, the pressure was released and reaction mixture extracted fromthe vessel with methylene chloride (2×2 mL) and water (2×2 mL). Thecombined layers were filtered and the organic layer separated, driedover NaSO₄ and solvent removed in vacuo to yield n-nonane as a colorlessoil (110 mg, 87%).

Nona-2,5,7-trione (170 mg, 1.00 mmol) was dissolved in 1M HOTf (5 mL)and added along with Pd/C (170 mg of 10 wt % Pd/C, 0.160 mmol Pd, 16 mol% Pd relative to substrate) and La(OTf)₃ (170 mg, 0.29 mmol) to astainless steel Swagelok equipped sample tube. The tube was thenpressurized with 100 psi H₂ and heated to 225° C. for 14 hours. Uponcooling, the pressure was released and reaction mixture extracted fromthe vessel with methylene chloride (2×2 mL) and water (2×2 mL). Thecombined layers were filtered and the organic layer separated, driedover NaSO₄ and solvent removed in vacuo to yield nonane as a colorlessoil.

Nona-2,5,7-trione (170 mg, 1.00 mmol) was dissolved in 0.1M HOTf (5 mL)and added along with Pd/C (170 mg of 10 wt % Pd/C, 0.160 mmol Pd, 16 mol% Pd relative to substrate) and La(OTf)₃ (170 mg, 0.290 mmol) to astainless steel Swagelok sample tube. The tube was then pressurized with100 psi H₂ and heated to 225° C. for 14 hours. Upon cooling, thepressure was released and reaction mixture extracted from the vesselwith methylene chloride (2×2 mL) and water (2×2 mL). The combined layerswere filtered and the organic layer separated, dried over NaSO₄ andsolvent removed in vacuo to yield nonane as a colorless oil.

Nona-2,5,7-trione (170 mg, 1.00 mmol) was dissolved in 1M HCl (5 mL) andadded along with Pd/C (170 mg of 10 wt % Pd/C, 0.160 mmol Pd, 16 mol %Pd relative to substrate) and La(OTf)₃ (170 mg, 0.290 mmol) to astainless steel Swagelok sample tube. The tube was then pressurized with100 psi H₂ and heated to 225° C. for 14 hours. Upon cooling, thepressure was released and reaction mixture extracted from the vesselwith methylene chloride (2×2 mL) and water (2×2 mL). The combined layerswere filtered and the organic layer separated, dried over NaSO₄ andsolvent removed in vacuo to yield nonane as a colorless oil.

Nona-2,5,7-trione (170 mg, 1.00 mmol) was dissolved in glacial aceticacid (5 mL) and added along with Pd/C (170 mg of 10 wt % Pd/C, 0.160mmol Pd, 16 mol % Pd relative to substrate) and Fe(OTf)₃ (170 mg, 0.480mmol) to a stainless steel Swagelok sample tube. The tube was thenpressurized with 100 psi H₂ and heated to 225° C. for 14 hours. Uponcooling, the pressure was released and reaction mixture extracted fromthe vessel with methylene chloride (2×2 mL) and water (2×2 mL). Thecombined layers were filtered and the organic layer separated, driedover NaSO₄ and solvent removed in vacuo to yield nonane as a colorlessoil as confirmed by GC-MS. ¹H NMR (400 MHz, CDCl₃) δ 1.29 (m, 14H), 0.88(s, 6H). ¹³C NMR (101 MHz, CDCl₃) δ 32.14, 29.73, 29.57, 22.81, 14.23.

Example 21

Unsaturated C₉ precursor (830 mg, 5.00 mmol) was dissolved in a 50% v/vsolution of acetic acid in H₂O (15 mL) and Pd/C added (83 mg of 10 wt %Pd/C, 0.08 mmol Pd, 1.6 mol % Pd relative to substrate). The solutionwas added to a round bottom flask and put under an atmosphere of H₂ andheated at 60° C. for 1 hour to yield saturated C₉ in situ. The flask wasthen equipped with a condenser, opened to the air and heated at 100° C.for 3 hours to yield a colorless solution. The aqueous layer wasneutralized with NaHCO₃ and extracted with dichloromethane (3×5 mL),dried over MgSO₄, filtered and solvent removed in vacuo to yieldnona-2,5,7-trione (817 mg, 96% yield).

What is claimed:
 1. A method of making a compound of formula I:

wherein R₁ is H or C₁₋₆alkyl; each R₂ is independently hydrogen orC₁₋₆alkyl; R₃ is H or C₁₋₆alkyl; R₄ is H, C₁₋₆alkyl, or substitutedC₁₋₆alkyl; n is 1, 2, 3, or 4; and m is 1, 2, 3, or 4; comprising:reacting a compound of formula A

with a compound of formula B

in the presence of pyrrolidinium salt, for a time and at a temperaturesufficient to provide the compound of formula I.
 2. The method of claim1, wherein the pyrrolidinium salt is pyrrolidinium acetate.
 3. Themethod of claim 1, wherein the temperature is ambient temperature. 4.The method of claim 1, wherein the time is between about 6 hours andabout 48 hours.
 5. The method of claim 1, wherein the method isperformed in the presence of at least one solvent.
 6. The method ofclaim 1, wherein the solvent is tetrahydrofuran, ethyl acetate,methanol, ethanol, propanol, isopropanol, diethyl ether, methylenechloride, water, or a combination thereof.
 7. The method of claim 1,wherein the method is performed in the absence of solvent.
 8. The methodof claim 1, wherein the molar ratio of A to B is about 1:1.
 9. Themethod of claim 1, wherein R₁ is H.
 10. The method of claim 1, whereinR₁ is methyl or ethyl.
 11. The method of claim 1, wherein each R₂ ishydrogen.
 12. The method of claim 1, wherein R₄ is hydrogen.
 13. Themethod of claim 1, wherein R₄ is substituted C₁₋₆alkyl.
 14. The methodof claim 1, wherein R₄ is —CH₂—OH
 15. The method of claim 1, wherein thecompound of formula A is


16. The method of claim 1, wherein the compound of formula A is


17. The method of claim 1, wherein the compound of formula A is:


18. The method of claim 1, wherein the compound of formula A is:


19. The method of claim 1, wherein the compound of formula B is


20. The method of claim 1, further comprising deoxidatively reducing thecompound of formula I to produce a saturated hydrocarbon.
 21. A compoundof formula I:

wherein R₁ is H or C₁₋₆alkyl; each R₂ is independently hydrogen orC₁₋₆alkyl; R₃ is H or C₁₋₆alkyl; R₄ is H, C₁₋₆alkyl, or substitutedC₁₋₆alkyl; n is 1, 2, 3, or 4; and m is 1, 2, 3, or 4; with the provisothat when R₁ is H, R₄ is C₁₋₆alkyl or substituted C₁₋₆alkyl.
 22. Thecompound of claim 21, wherein R₁ is H.
 23. The compound of claim 21,wherein R₁ is methyl or ethyl.
 24. The compound of claim 21, whereineach R₂ is hydrogen.
 25. The compound of claim 21, wherein R₄ ishydrogen.
 26. The compound of claim 21, wherein R₄ is substitutedC₁₋₆alkyl.
 27. The compound of claim 26, wherein R₄ is —CH₂—OH.
 28. Useof a compound of claim 21 in the production of saturated hydrocarbons.29. A process for synthesizing a fuel comprising deoxidatively reducinga compound of formula I:

wherein R₁ is H or C₁₋₆alkyl; each R₂ is independently hydrogen orC₁₋₆alkyl; R₃ is H or C₁₋₆alkyl; R₄ is H, C₁₋₆alkyl, or substitutedC₁₋₆alkyl; n is 1, 2, 3, or 4; and m is 1, 2, 3, or
 4. 30. A method ofmaking a compound of formula II:

wherein R₃ is H or C₁₋₆alkyl; R₄ is H, C₁₋₆alkyl, or substitutedC₁₋₆alkyl; and R₅ is C₁₋₁₆alkyl; comprising: reacting a compound offormula A

with a compound of formula C

in the presence of pyrrolidinium salt, for a time and at a temperaturesufficient to provide the compound of formula II.
 31. The method ofclaim 30, wherein the pyrrolidinium salt is pyrrolidinium acetate. 32.The method of claim 30, wherein the temperature is ambient temperature.33. The method of claim 30, wherein the time is between about 6 hoursand about 48 hours.
 34. The method of claim 30, wherein the method isperformed in the presence of at least one solvent.
 35. The method ofclaim 30, wherein the solvent is tetrahydrofuran, ethyl acetate,methanol, ethanol, propanol, isopropanol, diethyl ether, methylenechloride, water, or a combination thereof.
 36. The method of claim 30,wherein the method is performed in the absence of solvent.
 37. Themethod of claim 30, wherein the molar ratio of A to C is about 1:1. 38.The method of claim 30, wherein R₄ is hydrogen.
 39. The method of claim30, wherein R₄ is substituted C₁₋₆alkyl.
 40. The method of claim 30,wherein R₄ is —CH₂—OH.
 41. The method of claim 30, wherein R₅ isC₁₋₈alkyl.
 42. The method of claim 30, wherein the compound of formula Ais


43. The method of claim 30, wherein the compound of formula A is


44. The method of claim 30, wherein the compound of formula A is:


45. The method of claim 30, wherein the compound of formula A is:


46. The method of claim 30, wherein the compound of formula C is


47. The method of claim 30, wherein the compound of formula C is:


48. A process for synthesizing a fuel comprising deoxidatively reducinga compound of formula II:

wherein R₃ is H or C₁₋₆alkyl; R₄ is H, C₁₋₆alkyl, or substitutedC₁₋₆alkyl; and R₅ is C₁₋₁₆alkyl.
 49. A method of converting anoxygenated, unsaturated hydrocarbon or oxygenated, saturated hydrocarbonto a saturated hydrocarbon comprising: reacting the oxygenated,unsaturated hydrocarbon or oxygenated, saturated hydrocarbon withhydrogen under acidic conditions in the presence of a catalyst and aLewis acid for a time and at a temperature sufficient to provide thesaturated hydrocarbon.
 50. The method of claim 49, wherein the method isperformed in the presence of a protic acid.
 51. The method of claim 49,wherein the protic acid is acetic acid, hydrochloric acid, nitric acid,formic acid, sulfuric acid, trifluoromethanesulfonic acid, andcombinations thereof.
 52. The method of claim 49, wherein the pressureof the hydrogen is from about 15 psi to about 500 psi.
 53. The method ofclaim 49, wherein the pressure of the hydrogen is about 100 psi.
 54. Themethod of claim 49, wherein the method is performed at a temperature offrom ambient temperature to about 500° C.
 55. The method of claim 49,wherein the method is performed at a temperature of about 200° C. 56.The method of claim 49, wherein the catalyst is palladium, platinum,iron, cobalt, copper, chromium, or nickel.
 57. The method of claim 49,wherein the Lewis acid is Ln(X)n wherein Ln is a lanthanoid; X ishalide, triflate, bis(triflamide), C₁₋₆alkyl, aryl, amine, oxide,C₁₋₆alkoxide, or aryloxide; and n is 2 or
 3. 58. The method of claim 49,wherein the oxygenated, unsaturated hydrocarbon is:

wherein R₁ is H or C₁₋₆alkyl; R₄ is H, C₁₋₁₀alkyl, or substitutedC₁₋₁₀alkyl; and R₅ is C₁₋₁₆alkyl.
 59. The method of claim 49, whereinthe oxygenated, saturated hydrocarbon is

wherein R is C₁₋₆alkyl; R₁ is H or C₁₋₆alkyl; each R₂ is independentlyhydrogen or C₁₋₆alkyl; R₃ is H or C₁₋₆alkyl; R₆ is H or methyl; n is 1,2, 3, or 4; m is 1, 2, 3, or 4; and z is 1 to
 7. 60. The method of claim49, wherein the oxygenated, saturated hydrocarbon is


61. A method of making a compound of formula VI

wherein R₁ is H or C₁₋₆alkyl; each R₂ is independently hydrogen orC₁₋₆alkyl; R₃ is H or C₁₋₆alkyl; n is 1, 2, 3, or 4; m is 1, 2, 3, or 4;and z is 1 to 7; comprising reacting a compound of formula III

with maleic anhydride, an anhydride of the formula

maleic acid, fumaric acid, muconic acid, 2,5-furan dicarboxylic acid, ora dicarboxylic acid of the formula

in the presence of a Lewis acid or dehydrating agent; for a time and ata temperature sufficient to produce the compound of formula VI.
 62. Themethod of claim 61, wherein the anhydride of the formula

is succinic anhydride, glutaric anhydride, adipic anhydride, pimelicahydride, suberic anhydride, azelaic anhydride, or sebacic anhydride.63. The method of claim 61, wherein the dicarboxylic acid of the formula

is succinic acid, glutaric acid, adipic acid, pimelic acid, subericacid, azelaic acid, or sebacic acid.
 64. A method of making a compoundof formula IV:

wherein R₁ is H or C₁₋₆alkyl; each R₂ is independently hydrogen orC₁₋₆alkyl; R₃ is H or C₁₋₆alkyl; n is 1, 2, 3, or 4; m is 1, 2, 3, or 4;and R is C₁₋₆alkyl; comprising reacting a compound of formula III

with an anhydride of the formula R—C(O)—O—C(O)—R in the presence of aLewis acid, for a time and at a temperature sufficient to produce thecompound of formula IV.
 65. A method of making a compound of formula V

wherein R₁ is H or C₁₋₆alkyl; each R₂ is independently hydrogen orC₁₋₆alkyl; R₃ is H or C₁₋₆alkyl; n is 1, 2, 3, or 4; m is 1, 2, 3, or 4;and R₆ is H or C₁₋₂alkyl; comprising reacting a compound of formula III

with a compound of formula

in the presence of a Lewis acid or protic acid, for a time and at atemperature sufficient to produce a compound of formula V.